JPH06122835A - Subdivided pigment dispersion, water-base pigment suspension, production of dispersion, and water-resistant ink containing dispersion produced thereby - Google Patents

Abstract

A dispersion of a finely divided pigment in a composition of water, one or more water-compatible resins and, as dispersant, a polycyclic aromatic compound having a water-solubilising poly(C2-4-alkyleneoxy) chain containing from 3 to 50 alkyleneoxy groups, characterised in that the dispersion contains from 3% to 30% by weight or resin with respect to the total weight of water and resin in the dispersion. The dispersion is suitable for the preparation of water-borne paint and inks.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to aqueous dispersions, particularly water-compatible resins and water-borne materials.
Grinding in the production of paints or inks-based (mill
-Base) and an aqueous dispersion of a pigment containing a suitable dispersant.

[0002]

Grinding for water resistant paints and inks-
The base is usually produced by pulverizing the paint and an aqueous dispersion of one or more resins in order to subdivide the paint and ensure that it is evenly distributed in the aqueous resin medium.
The resin used should be water-compatible.
Able but optimal paint or ink (especially packaging ink)
It is recognized that in order to obtain the performance (particularly water resistance), the resin preferably used is not water-soluble. Suitable water-insoluble resins can usually be described as water-dilutable, water-dispersible or emulsifiable. However, it is known that water-insoluble resins generally do not provide sufficient dispersing power to ensure that the pigment is well dispersed, and therefore adversely affect the performance of the resulting paint or ink. It is a common practice to include the water-soluble resins that they have, which generally give better dispersancy than water-insoluble resins, in such mill-bases.

[0003]

It has now been found that the use of specific classes of dispersants can provide mill-bases with pigments that disperse well. This makes it possible to produce a well-dispersed ground-base which contains water, a water-insoluble resin, a pigment and a dispersant and contains little or no water-soluble resin. Surprisingly, this dispersant does not have a detrimental effect on paint or ink performance in the same way as water-soluble resins.

[0004]

According to the present invention, water,
One or more water-compatible resins and 3 to 5 as a dispersant
Has 0 alkyleneoxy group poly be water-soluble - containing polycyclic aromatic compound having a (C ₂ -C ₄ alkyleneoxy) chain, a dispersion of pigments subdivided, the dispersion Is 3% to the total weight of water and resin in it.
A dispersion is provided which is characterized in that it comprises 30% by weight of resin.

The pigment is a substantially water-insoluble colorant that can be used to color water resistant paints or inks. Such pigments generally have a color index (3rd
Version) and the subsequent addendum and addendum. Suitable pigments are those customary in water-resistant coatings and inks such as copper phthalocyanine, carbon black, quinacridone, dianthraquinone, monoazo pigments, vat dyes, dioxazine violet, diketopyrrolopyrrole, titanium dioxide and iron oxide. is there. The particle size of the subdivided pigment particles is preferably <5 μm and more preferably 1 μm
It is the following.

The water-compatible resin can be either a water-soluble or water-insoluble polymer or mixtures thereof.
However, it is preferred that each resin is water insoluble. This is because such resins are generally known to provide paints or inks with better durability than water-soluble resins.

Examples of such resins are acrylic, styrene-acrylic, polyester, polyurethane, acrylic-polyurethane, vinyl acetate, vinyl chloride polymers and copolymers and water dispersible alkyd resins. Suitable resins are acrylic, styrene-acrylic, polyester,
Polyurethane and acrylic-polyurethane resins.
The dispersant is preferably of the formula: (A-X-Y) _p- R where A is a polycyclic aromatic group; X is -O-, -C.
OO -, - S -, - NH- and be a bridging group selected from -NY-; Y is _{- (C 3 H 6 O)} m - (C 2 H 4 O) n -
Or _{- (C 2 H 4 O)} n - (C 3 H 6 O) m - a it is; m is 0
~ 2n; m + n is 3 to 50; p is 1 or 2
By and; R If p is 1, H, alkyl or -PO ₃ M ₂ 1 to 4 carbon atoms; R if p is 2, = PO ₃
M; and M is H, metal, or optionally substituted ammonium].

The value of p is 1, so that the dispersant preferably contains a single (A-X-Y) group.

The polycyclic aromatic group A preferably has 2 or 3 fused rings, more preferably a naphth-1-yl or naphth-2-yl group, more preferably the latter. And these are halogen, alkyl having 1 to 4 carbons or 1 carbon
It may have an alkoxy substituent of up to 4 but is preferably unsubstituted. The bridging group X is preferably -O- or -CO-O.
And the dispersant is preferably naphthol, especially naphtho-
Obtained by alkoxylation of 2-ole. m + n is preferably 3 to 30, in particular 5 to 15, more particularly 8 to
Twelve. The value of m is preferably a 0 to n, and more preferably 0, so that the poly (C ₂ ~C ₄ - alkyleneoxy) chain is a polyethyleneoxy chain. Particularly good results, naphth-2-yloxy - is achieved by _{(C 2 H 4 O) 10} H. This type of dispersant is described in British Patent No. 2,0
No. 60,715. When M is a metal, it is preferably an alkali metal such as sodium, potassium. When M is optionally substituted ammonium, this is preferably NQ ₄ , where each Q is independently hydrogen, C 1-20 alkyl, hydroxy-C 1-6 alkyl, Benzyl or two Q together with a nitrogen atom form a 5 or 6 membered ring such as piperidine, piperazine or morpholine.

The dispersions according to the invention preferably contain at least 10%, and preferably up to 80% by weight of pigment, based on the total dispersion. When the pigment is organic or normal carbon black having a surface area of 200 m ² / g or less, the dispersion preferably has 20% to 50% by weight of the pigment, but when the pigment is an inorganic substance, it is dispersed. The liquor may preferably contain from 40% to 70% by weight of pigment, based on similar criteria. However, high or very high surface area carbon black (> 200 m ²
/ G surface area), the dispersion is as low as 3% based on the same criteria, more preferably 5%.
% To 15% pigment can be contained and the amount of dispersant is preferably from 50% to 100% by weight, based on the weight of the pigment. The dispersion contains at least 1% by weight, preferably up to 100% by weight, of dispersant, based on the weight of the pigment.
When the pigment is an organic pigment or carbon black with respect to the weight of the pigment in the dispersion, the dispersion more preferably contains 5% to 50% by weight of a dispersant, and when the pigment is an inorganic pigment, it is dispersed. The liquor preferably contains 1% to 10% by weight of dispersant. The dispersion preferably contains at least 5% by weight and more particularly at least 10% by weight of resin, based on the total amount of water and resin in the dispersion. The dispersion preferably contains up to 25%, more preferably up to 20% resin based on the same criteria.

As already indicated, this composition comprises higher amounts of water-compatible resins and / or preservatives, stabilizers, defoamers conventionally added to water and water resistant paints and inks. And coalescing agents
It is suitable as a grinding base for producing water resistant resins and inks by mixing with other ingredients such as. Water resistant coatings and inks containing the dispersions produced according to the invention are another feature of the invention.

In the present invention, a water-resistant coating having particularly useful properties as compared with conventional coatings and inks with respect to durability, gloss and humidity resistance of the coating or ink film after using and drying the coating or ink. It has also been found that it enables the production of mill-bases, which are high pigment contents with good flowability (low viscosity) that can be used for producing inks.

The present dispersants have superior paint and ink properties with respect to gloss and foam resistance as compared to other dispersants having equivalent HLB values, and gloss and durability as compared to water soluble dispersible resins. Enable the manufacture of.

The dispersion can be prepared by any method used for the preparation of mill-bases, provided that it contains all the ingredients as defined above.
Thus, for example, one or more resins are dispersed and / or dissolved in water and the dispersants and pigments are in a coarse or unmilled state (which has an average particle size of preferably 5
Micrometer or more, more specifically 10 micrometers or more) is added to the mixture and then subjected to high shear treatment, such as beads or to produce a uniform dispersion of finely divided pigment in an aqueous medium. Ball crushing can be performed.

A premilled base (p) containing a suspension of unmilled pigment in water containing a water compatible resin and a dispersant.
The re mill-base) is also novel and forms another feature of the invention.

Another advantage of the present invention is that the dispersion does not tend to foam in the mill-base, which makes it easier to mill and operate and has a detrimental effect on paint or ink performance. It is to avoid or minimize known defoamers. This further reduces or allows the use of water-soluble resins, which have a detrimental effect on the durability and / or humidity resistance of the resulting paint or ink film.

[0017]

The invention is further illustrated by the following examples, in which all parts and percentages are by weight unless otherwise indicated. The dispersants in the examples are identified as follows.

2-Naphthol-10EO 2-Naphthol 1 mol / ethylene oxide 10 mol condensate 1-Naphthol-10EO 1-naphthol 1 mol / ethylene oxide 10 mol condensate 2-naphthol-15EO 2-naphthol 1 mol / ethylene oxide 15 moles of a condensation product of 2-naphthoyl-PEG (350) -OCH ₃ 2-naphthoyl chloride 1 mole and molecular weight of 350 methemoglobin key polyethylene glycol 1 mol of a condensate of 2-naphthol -5PO-5EO first 2-naphthol 1 Moles of propylene oxide and 5 moles of propylene oxide followed by condensation with 5 moles of ethylene oxide 2-naphthol-10PO-11EO First, 1 mole of 2-naphthol and 10 propylene oxides.
Mol condensed and then ethylene oxide 11 mol of naphthoic acid + 20EO-11PO-OCH ₃ 2- naphthoic acid 1 mol of 1 mole of methanol and propylene oxide 10 mol those condensed, then, obtained by reacting 20 moles of ethylene oxide Condensation product of 1 mol of block copolymer 2-naphthol-5EO Condensation product of 2- mol of ethylene oxide and 1 mol of 2-naphthol reacted with phosphorus pentoxide at a ratio of phosphoric group to phosphorus of 1: 1 10EO Phosphate A condensate of 10 mol of ethylene oxide and 1 mol of 2-naphthol reacted with phosphorus pentoxide at a ratio of hydroxy groups to phosphorus of 1: 1.

Example 1 A glass bottle with a screw cap having a volume of 120 ml was charged with dimethylquinacridone MONOLITE Rubine 3.
B (Zeneca Colors) 7.0 g, water 1
1.3g, 45% solid acrylic copolymer emulsion NE
OCRYL XK90 (Zeneca Resins)
11.67 g, modified polysiloxane defoamer, DE
HYDRAN 1293 (Henkel) 0.32 g,
Monopropylene glycol 3.76g and 2-naphthol-10EO 0.95g 3mm glass beads 125
Fill with g and use Red Devil Shaker (Re
mill for 45 minutes on a dDevil shaker,
A mill-base was prepared.

The highly flowable milling base obtained-NE
Add 70.0 g of OCRYL XK90 to dilute,
A paint was formed. The paint was used on a metal panel primed with a wire wound coating bar (100 micrometer wet film thickness). After air drying for 90 minutes and then hot drying at 120 ° C. for 30 minutes, 2 of the resulting flat coating was obtained.
The 0 ° gloss value was measured. The results are shown in Table 1.

Examples 2-9 The procedure detailed in Example 1 was repeated substituting the following dispersants for 2 -naphthol-10EO. In each case a highly flowable mill-base was obtained and the 20 ° gloss of the final paint film was measured. The results are shown in Table 1.

Table 1 Example No. Dispersing agent Gloss (20 °) 1 2-naphthol-10EO 62.70 21-naphthol-10EO 62.08 3 2-naphthol-15EO 55.42 42 2-naphthoyl-PEG ( 350) -OCH ₃ 60.38 5 2- naphthol -5PO-5EO 66.24 6 2- naphthol -10PO-11EO 63.12 7 2- naphthoic acid _{+ 20EO-11PO-OCH 3 58.50} 8 2- naphthol -5EO Phosphate 63.6899 2-Naphthol-10EO Phosphate 58.58 Comparative Example 1 Example 1 was repeated, substituting water for 2-Naphthol-10EO. No free-flowing mill-base was obtained. The final coating contained many undispersed particles and had a 20 ° gloss value of 4.12 units.

Comparative Example 2 Example 1 was repeated, substituting water for the emulsion of the acrylic copolymer in the ground-base. The grind-base was more fluid than the grind-base of Example 1, but 2 of the final paint film.
The 0 ° gloss was 52.84 units. This paint was prepared from the paint of Example 1 in terms of color strength visually evaluated by diluting 1:25 with a white acrylic copolymer emulsion paint and cohesion resistance evaluated by cross-brushing the coated panel. Was also inferior.

Example 10 2-Naphthol-10EO (0.95 g) was dissolved in 11.3 g of water in a bottle with a screw cap having a volume of 120 ml. The solution was shaken vigorously for 15 seconds and the height of bubbles on the surface of the solution was measured. Then, in this bottle NEO CRYL X
K90 11.67 g, propylene glycol 3.76
g, 3mm glass beads 125g and MONOLITE
Rubine 3B 7.0 g was added and the mixture was milled for 45 minutes on a red devil shaker. The height of bubbles on the liquid surface was measured immediately after crushing. The highly flowable dispersion thus obtained was diluted and used in panels as described in Example 1 to measure 20 ° gloss values. The results are shown in Table 2.

Comparative Examples 3 and 4 2-Naphthol-10EO was mixed with nonylphenol-15.
EO, SYNPERONIC NP15 (ICI) (Comparative Example 3) and C13 / 15 synthetic alcohol + 11EO,
SYNPERONIC A11 (ICI) (Comparative Example 4)
The method of Example 10 was repeated, substituting

Dispersant SYNPERONIC NP15
(HLB = 15.39) and SYNPERONIC A
11 (HLB = 14.36) HLB (calculated by Griffin's formula-ref: Porter MR, Han
dbbook of Surfactants, Blac
Kie, 1991, p. 42) is 2-naphthol-10.
These comparative examples were selected on the basis of being very close to the calculated value of EO (HLB = 15.65). The results are listed in Table 2.

[0027] Table 2 solution foam height grinding - base foam height 20 ° gloss value Example 10 foam height 0 5 mm 64.52 Comparative Example 3 35 mm 35 mm 57.60 Comparative Example 4 65 mm 35 mm 57 .64 Example 11 2-Naphthol-10EO (0.59 g) was dissolved in 14.42 g of water in a 120 ml volume bottle with a screw cap. The solution was shaken vigorously for 15 seconds and the foam height above the liquid surface was measured. NEOCRYL XK90 9.09g,
Propylene glycol 3.76 g, DEHYDRAN
1293 0.32 g, 3 mm glass beads 125 g and C.I. I. Pigment Green 36 MONASTRAL
9.79 g of Green 6Y (ICI) was added to the bottle and the mixture was milled on a Red Devil shaker for 45 minutes.
The highly fluid dispersion thus obtained is NEOCRY
The paint was diluted with 93.0 g of LXK90 and applied to a panel as in Example 1 and the 20 ° gloss value was measured. The results are listed in Table 3.

Comparative Examples 5 and 6 2-naphthol-10EO was mixed with SYNPERONIC N.
P15 (Comparative Example 5) and SYNPERONIC A11
The method of Example 11 was repeated, substituting each in (Comparative Example 6).

The results are listed in Table 3.

[0030] Example 1 In Table 3 solution foam height 20 ° gloss value Example 11 14 mm 53.02 Comparative Example 5 75 mm 47.09 〃 6 75 mm 42.84 Example 12 to 17 and Comparative Example 7 The following formulation The mill-base is prepared, diluted in paint, coated and tested as detailed in. The results obtained are listed in Table 4.

Table 4 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 7 Ground- Base 2-Naphthol-10EO 1.01 1.89 2.46 0.15 1.02-Water 7.19 12.80 5.59 6.02 3.74 4.76 NEOCRYL XK90 11.67 8.37 11.67 4.37 17.92 17.92 Propylene Glycol 3.76 3.62 3.76 2.50 2.70 2.70 DEHYDRAN 1293 0.32 0.31 0.32 0.21 0.23 0.23 Pigment A 1.05 Pigment B 6.75 Pigment C 11.20 Pigment D 10.00 Pigment E 25.60 25.60 Let Down NEOCRYL XK90 35.00 56.00 119.00 76.75 53.20 53.20 Gloss (20 °) 68.82 63.76 62.78 15.70 Flowability Flow Flow Flow Flow Flow Flow Viscosity + Slightly crushed The pigments used are: Pigment A-C. I. Pigment Black 7 Black FW
200 (Degussa) Pigment B-C. I. Pigment Blue 15: 2 MONA
STRAL BLUEFNX (ex ICI) Pigment C-C. I. Pigment Red 177 CROMO
PHTAL Red A2B (Ciba Geigy) Pigment DC. I. Pigment Red 101 BAYFE
RROX Red110M (Bayer) Pigment E-C. I. Pigment White 6 TIOXID
E TR92 (Tioxide) Example 17 A coating was prepared according to the method of Example 1 and then applied to an uncoated aluminum panel with a wire wound coating bar (100 micrometer wet film thickness).
After air drying, the panels were left at room temperature (21 ± 2 ° C.) for 4 days to cure and release all volatile components. Measure the 20 ° gloss of the paint film and set the panel to 80.
It was soaked in water at ℃ for 24 hours. The coating then shrinks at regular intervals and examined for blisters or signs of loss of adhesion.
The results are listed in Table 6.

COMPARATIVE EXAMPLES 8-11 The procedure of Example 17 was followed using a paint prepared from the formulation of Table 4 which replaces the dispersant in the ground-base and the water-insoluble resin with a water-soluble dispersant resin. I repeated. The details of the resin used are as follows: a) NEOCRYL BT24 (Zeneca Res)
ins), 50% solution of 2-dimethylamino-ethanol (DMA
45% solid acrylic copolymer suspension, solubilized by the addition of E) to pH 9 ± 1; b) JONCRYL 61 (SC Johnso).
n), 35% solids acrylic resin solution.

Table 5 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 a) NEOCRYL BT24 11.67 15.95 b) JONCRYL 61 15.00 20.50 water 11.34 6.42 8.92 3.42 50% DMAE solution 0.91 1.55 DEHYDRAN 1293 0.32 0.32 0.32 0.32 propylene glycol 3.76 3.76 3.76 3.76 CI Pigment Red 122 7.00 7.00 7.00 7.00 Let Down NEOCRYL XK90 70.00 70.00 70.00 70.00 Table 6 shows the results.

[0034]Table 6 Example Mitsuzawa Paint film evaluation 17 64.80 After 24 hours-coating remains intact without blister, shrinkage or loss of adhesion Comparative Example 8 53.43 After 10 minutes-Extremely fine blisters are 100% covered Comparative Example 9 39.42 10 minutes later-100% covered by blisters with a diameter of 0.5-1.0 mm Comparative Example 10 62.88 10 minutes later-2-3 mm Blister strips all circles. On the diameter panel edge Comparative Example 11 58.68 10 minutes later-edge 2-3 mm, center 1-2 Milliblister covers 100% Example 18 2-naphth in a bottle with a screw cap with a volume of 60 ml.
Tol-10EO (0.48g) dissolved in 7.69g water
did. Shake the solution vigorously for 15 seconds to adjust the foam height above the surface of the liquid.
It was measured. Then, 42% solid styrene-acrylic copolymer
Polymer Suspension NEOCRYL XK62 (Zenec
a Resins) 5.84g, 3mm glass beads
65g, and MONOLITE Ruby 3B
3.5 g was added to this bottle and the mixture was mixed with red devi
Grind for 45 minutes on a le shaker. Bubble height on liquid surface
Was measured immediately after grinding. High degree obtained in this way
Dynamic dispersion, NEOCRYL XK62 35.0
g and ethylene glycol monobutyl ether 2.0 g
The mixture prepared from was added to the paint to dilute it. paint
Was used on the panel as described in Example 1 and was exposed to 20 ° light.
The swamp was measured. The results are listed in Table 7.

Comparative Examples 12 and 13 2-Naphthol-10EO was added to nonylphenol-15E.
O, SYNPERONIC NP15 (ICI) (Comparative Example 12) and C13 / 15 synthetic alcohol + 11EO,
SYNPERONIC A11 (ICI) (Comparative Example 1)
The procedure of Example 18 was repeated substituting 3). The results are listed in Table 7.

[0036] Table 7 solution foam height grinding - base foam height 20 ° gloss value Example 18 8 mm 5 mm 57.48 Comparative Example 12 60 47.78 Comparative example mm air is supplied to the entire 13 60 mm Full of bubbles 48.06 Comparative Example 14 Milling-Example 18 was repeated substituting water for the styrene-acrylic copolymer emulsion in the base. The 20 ° gloss of the final paint film was only 52.06 units and the paint film contained a large number of large undispersed pigment particles.

Example 19 2-Naphthol-1 in a screw bottle with a volume of 60 ml.
0EO (0.48g) was dissolved in 9.66g of water. The solution was shaken vigorously for 15 seconds and the foam height above the liquid surface was measured.
Next, URADIL SZ251 G3Z-70 (DS
M Resins) 3.86 g, 70% active saturated polyester resin dissolved in a butyl glycol / water / triethylamine mixture, 65 g of 3 mm glass beads and M
ONOLITE Rubine 3B (ICI) 3.5
g was added to the bottle and the mixture was milled on a Red Devil shaker for 45 minutes. The foam height on the liquid surface was measured immediately after grinding. The highly fluid dispersion thus obtained is
URADIL SZ251G3Z-70 12.27
g, CYMEL 303 (American cyanamide) 6.
24 g, 100% active low molecular weight melamine-formaldehyde resin, 2-dimethylaminoethanol 0.14 g
And a mixture prepared from 0.70 g of water was added to dilute the paint. This paint was applied to a metal panel primed with a wire-wound coating bar (100 micrometer wet film thickness) and dried at 160 ° C for 15 minutes and the 20 ° gloss value of the resulting flat film was measured. The results are listed in Table 8.

Comparative Examples 15 and 16 2-Naphthol-10EO was added to nonylphenol-15E.
O, SYNPERONIC NP15 (ICI) (Comparative Example 15) and C13 / 15 synthetic alcohol + 11EO,
SYNPERONIC A11 (ICI) (Comparative Example 1)
The method of Example 19 was repeated, substituting each in 6). The results are listed in Table 8.

[0039] Table 8 solution foam height grinding - base foam height 20 ° gloss value Example 19 7 mm foam None 75.76 Comparative Example 15 32 mm 32 mm 69.86 Comparative Example 16 60 mm 35 mm 56.64 Comparative Example 17 Milled-URADIL SZ251 G3Z-7 in Base
Example 19 was repeated, substituting 0 for water, and the 20 ° gloss of the final paint film was only 54.98 units.

Example 20 Water 47 g, 2-naphthol-10EO 3.0 g, JO
NCRYL 74 20 g, (SC Johnso
n), 47% solids rheology controlled acrylic polymer emulsion and C.I. I. Pigment Red 5
7: 1 (LITHOL Rubine 4569, ex
30 g of the mixture (BASF) was dispersed with a high speed disc stirrer at 3100 rpm and then ground with a Red-Devil shaker. After standing for 7 days, the dispersion retained its excellent water-thin rheology, 0.5% SURFYNOL 104E.
(AirProducts), Pigment Wetting Agent (wetti
defoaming surfactants commonly used as ng agents), water containing grinding aids and defoamers in printing inks and mixtures made from JONCRYL 74, 2,4,
A final ink was prepared by adding a solution containing a 50% ethylene glycol solution of 7,9-tetramethyl-5-decyne-4,7-diol to give a final ink. The ink was printed on polyethylene paper with an Analox roller and pulled down onto the card using a wire wound bar (24 micrometer wet film thickness). The ink was then tested for optical density, gloss, opacity and bubble formation and the results are shown in Table 9.

Comparative Example 18 49 g of water, 1.0 g of SURFYNOL 104E, J
ONCRYL 7420 g and C.I. I. Pigment Red 57: 1, LITHOL Rubine 4569 (B
ASF) 30 g of the mixture was dispersed at 3100 rpm using a high speed disc disperser and then ground on a Red-Devil shaker. The resulting dispersion was very viscous and did not reach an acceptable grind. An additional 10 g of water was required to reduce the viscosity and allow effective grinding. After standing for 7 days, the rheology of the dispersion is thixotropic, which suggests that JONCRYL
By adding a mixture made from water containing 74 and 0.5% SURFYNOL 104E, the amounts being adjusted so that the ink contains the same amount of pigment, resin and water as the ink of Example 20. The final ink. The ink was coated and tested as in Example 20. The results obtained are shown in Table 9.

Table 9 Example 20 Comparative Example 18 Optical Density 1.68 1.45 60 ° Gloss 38.1 32.9 Opacity (5 = Maximum Cover Value) 5 2 Bubbles (5 = All Bubbles) 2 3 Example 21 and Comparative Example 19 Tenth The procedure of Example 20 was repeated using the formulation given in the table and the results obtained are listed in Table 11.

Table 10 Example 21 Comparative Example 19 C.I. I. Pigment Blue 15: 4 (1) 30g 30g JONCRYL 74 20g 20g 2-naphthol-10EO 2.25g SURFYNOL 104E 1.0g SOLSPERSE 12000 (2) 0.75g water 47g 49g (1) IRGALITE BLUE GLVO (C)
a-Geigy) (2) Sulfonated Copper Phthalocyanine (ICI) Table 11 Example 21 Comparative Example 19 Milling-Base viscosity (after 7 days) Thin water non-fluidity Optical density 1.86 1.68 60 ° Gloss 39 .8 38.2 Opacity (5 = maximum coverage) 5 2 Examples 22-24 and Comparative Examples 20-22 The optimal ink formulations given in Table 12 are the mill-base for each individual ink formulation. It was obtained by extensive pre-evaluation of the amounts of pigments and agents in it. Milling-base is
3 with 3 mm glass beads on a lettuce devil shaker
It was produced by shaking for 0 minutes. The flowable dispersion thus obtained is let down by adding a mixture prepared from the components indicated in the let down formulation and then drawn on a polyethylene sheet with a wire winding bar (6 μm wet film thickness). Then, it was further coated on paper with an experimental gravure printing machine. The films were tested after air drying and the results obtained are shown in Table 13.

Twelfth Table Example 22 Comparative Example 20 Example 23 Comparative Example 21 Example 24 Comparative Example 22 Crush-based CI Pigment Yellow 13 (1) 25.00 12.50 CI Pigment Yellow 28 (2) 25.00 25.00 CI Pigment Black 7 (3) 27.50 27.50 2-naphthol -10EO 1.00 1.00 3.44 JONCRYL 8051 (4 ) 19.42 19.42 19.42 19.42 19.42 19.42 water 54.54 68.04 54.25 55.25 49.60 53.04 FOAMASTER DF177 -F (5) 0.04 0.04 0.04 0.04 DEHYDRAN 1293 0.33 0.33 letdown JONCRYL 8051 133.20 2.20 133.20 133.20 155.40 155.40 JONWAX 35 (6) 10.20 1.70 10.20 10.20 11.90 11.90 Carbitol (7) 6.60 1.10 6.60 6.60 7.70 7.70 (1) PERMANENT Yellow GR (Hoechs
t) (2) LUTETIA Yellow JR (Zeneca C
(3) PRINTEX 35 (Degussa) (4) 45% solids rheology controlled acrylic polymer emulsion (SC Johnson) (5) propoxylated alcohol defoamer (Henk)
el) (6) 35% solid polyethylene wax emulsion (S.
C. Johnson) (7) 2- (2-ethoxyethoxy) ethanol Table 13 Example 60 ° Gloss Optical density Example 22 11.5 1.31 Comparative Example 20 10.0 1.05 Example 23 18.8-Comparative Example 21 16 .2-Example 24 27.2 1.39 Comparative Example 22 22.0 1.32 The effect of the agent on the adhesion and water sensitivity of the ink was evaluated as follows. After air drying for 2 hours, the printed strips were cut from the polyethylene pattern. The pieces were held between the hands, which were about 1 cm apart. The exposed portion of the ink was placed under a moving cold tap and the hand was rotated 50 times in the opposite direction to "crinkle" the ink film. The test was repeated using the corresponding comparative inks to compare the ink loss from the two films. After air-drying for 2 hours, "crimp (cri
Another test was carried out with another piece of polyethylene that had been soaked in water for 2 hours before the "inkle)" test. The inks produced in Examples 22 and 23 were in both tests better than the corresponding inks in the Comparative Example. It showed good adhesion and water resistance In Example 24, the use of the agent had no detrimental effect on adhesion or resistance compared to the inks in the comparative examples.

Example 25 2-Naphthol-10EO (0.95 g) was dissolved in 9.10 g of water in a screw bottle with a volume of 60 ml. Then, in this bottle, 33% solid aromatic urethane acrylic copolymer dispersion, NEOPAC E106
(Zeneca Resins) 3.95 g, 3 mm glass beads 65 g, and MONOLITE Rubin
3.5 g of e 3B (ICI) was added and the mixture was milled on a Red Devil shaker for 45 minutes. 35.15 g of NEOPACE106 was obtained from the dispersion liquid thus obtained.
It was diluted to a paint by adding a mixture prepared from 1.85 g of propylene glycol. The paint was applied to the panel as described in Example 1 and the 20 ° gloss value was measured to be 33.96 units.

Comparative Example 23 Milling-Example 25 was repeated, substituting water for NEOPAC E106 in the base. Diluting the mill-base into paint resulted in extreme pigment agglomeration (commonly known as pigment shock). As a result, the final paint film was covered with large undispersed pigment particles with a 20 ° gloss value of only 1.58 units.

Example 26 2-Naphthol-10EO (0.48 g) was dissolved in 10.20 g of water in a screw cap bottle with a volume of 60 ml. Then, NEO CRYL XK901.28
g, DEHYDRAN 1293 0.16 g, propylene glycol 1.88 g, 3 mm ganis beads 65
g and MONOLITE Rubine3B (ICI)
3.5 g was added to the bottle and the mixture was milled for 45 minutes on a Red Devil shaker. 35 g of NEOCRYL was added to the highly fluid dispersion thus produced.
The paint was diluted by adding XK90. The paint was applied to a panel as described in Example 1 and the 20 ° gloss value was measured to be 55.38 units.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C09B 67/46 B 7306-4H C09C 3/08 PBU 8218-4J C09D 5/02 PPU 6904-4J 7 / 06 PSL 7211-4J 11/02 PTF 7415-4J 17/00 PUJ 7415-4J

Claims (10)

[Claims] 1. A water-soluble poly (C ₂ -C ₄ -alkyleneoxy) chain having at least one resin compatible with water and 3 to 50 alkyleneoxy groups as a dispersant. A dispersion of subdivided pigments having a composition of a polycyclic aromatic compound having a content of 3% by weight to 30% by weight of resin with respect to the total weight of water and resin in the dispersion. A dispersion characterized by: 2. The dispersant has the following formula: (A-X-Y) _p- R [wherein A is a polycyclic aromatic group; X is -O-, -C.
(O) O -, - S -, - N (H) - and -N (Y) - be a bridging group selected from; Y is _{- (C 3 H 6 O)} m - (C 2
H ₄ O) - or _{- (C 2 H 4 O)} n - (C 3 H 6 O) m - a is; m is from 0 3n; m + n is 3 from 50; p is 1 or 2 There; R is when p is 1, H, alkyl or -PO ₃ M ₂ 1 to 4 carbon atoms; R is p is 2
Where = PO ₃ M and M is H, metal or appropriately substituted ammonium]. 3. The dispersant is naphth-2-yloxy- (C
The dispersion according to claim 2, which is ₂ H ₄ O) ₁₀ H. 4. The dispersion according to claim 1, wherein the resin is selected from acrylic resin, styrene acrylic resin, polyester resin, polyurethane resin and acrylic-polyurethane resin. 5. The dispersion according to claim 1, wherein the resin is water-insoluble. 6. One or more resins compatible with water and 3 to 50.
Number of alkylene having oxy group, poly to the water solubility (C ₂ ~C ₄ - alkyleneoxy) aqueous suspension of unmilled pigment containing polycyclic aromatic compound having a chain. 7. The method for producing a dispersion according to claim 1, wherein the aqueous suspension obtained according to claim 6 is subjected to high shear treatment. 8. A water resistant coating comprising the dispersion according to any one of claims 1 to 5. 9. A water-resistant ink comprising the dispersion liquid according to claim 1. 10. A water-resistant packaging ink comprising the dispersion liquid according to claim 1.